CN109518278A - A kind of method of richness nitrogen atmosphere enhancing boron nitride pellicle p-type electric-conducting doping - Google Patents

A kind of method of richness nitrogen atmosphere enhancing boron nitride pellicle p-type electric-conducting doping Download PDF

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CN109518278A
CN109518278A CN201811339108.8A CN201811339108A CN109518278A CN 109518278 A CN109518278 A CN 109518278A CN 201811339108 A CN201811339108 A CN 201811339108A CN 109518278 A CN109518278 A CN 109518278A
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boron nitride
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nitrogen atmosphere
warm area
rich nitrogen
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CN109518278B (en
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蔡端俊
王跃锦
刘国振
郝卓然
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Xiamen University
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/38—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/342—Boron nitride
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B31/00—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor
    • C30B31/06—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor by contacting with diffusion material in the gaseous state
    • C30B31/08—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor by contacting with diffusion material in the gaseous state the diffusion materials being a compound of the elements to be diffused

Abstract

The invention discloses a kind of methods of rich nitrogen atmosphere enhancing boron nitride pellicle p-type electric-conducting doping, acceptor level first by first promoting to form the vacancy B in hexagonal boron nitride crystal under rich nitrogen atmosphere, displacement doping by Mg in hexagonal boron nitride lattice again, the two carries out in order, and then enhances hexagonal boron nitride film p-type conductivity energy.

Description

A kind of method of richness nitrogen atmosphere enhancing boron nitride pellicle p-type electric-conducting doping
Technical field
The present invention relates to a kind of methods of rich nitrogen atmosphere and Mg the doping successively doping of enhancing boron nitride pellicle p-type electric-conducting.
Background technique
Hexagonal boron nitride (h-BN), referred to as " white graphite alkene " have the structure of similar graphene: a monatomic thickness The h-BN of degree is the two-dimensional film of sp2 hydridization, is made of boron and the alternately arranged honeycomb lattice structure of nitrogen-atoms.With high heat Conductive performance, mechanical strength, optical clarity, chemical stability and deep ultraviolet lasing, therefore there are many potential applications. Especially in deep ultraviolet (DUV) optoelectronic areas, due to its big band gap (~6eV) and close to zero polarization field and have very Good application prospect.And h-BN only has the thin scale of atom level, therefore, the research for this ultra-thin low-dimensional materials meets Epoch require the size of material and device and gradually tend to ultra-thin, ultralight, extra small, super transparent developing direction, for two The further investigation of dimension Semiconductor Optoeletronic Materials is of great significance.
H-BN's is unique in that its uncommon p-type doping tendency, i.e. the resistivity of the p-type h-BN of Mg doping than The resistivity for mixing the AlN of Mg doping is much smaller.Had the result shows that, using Mg adulterate h-BN can detecte out p-type Conductance: conductive current reaches~12 μ A and hole concentration~1.7 × 1014cm-2, but be difficult to be improved again.In addition, Theoretical calculation shows that these hole concentrations mostly come from the Mg acceptor impurity and B vacancy defect of part activation, studies have shown that This point defect --- the vacancy B, can be used as acceptor level in h-BN, and its energy level more than valence band~150meV.
Summary of the invention
It is thin it is an object of the invention in place of overcome the deficiencies in the prior art, provide a kind of rich nitrogen atmosphere enhancing boron nitride The method of film p-type electric-conducting doping, solves the problems in above-mentioned background technique.
The technical solution adopted by the present invention to solve the technical problems is: a kind of richness nitrogen atmosphere enhancing boron nitride pellicle p-type The method of conductiving doping, this method form the vacancy B by promoting under rich nitrogen atmosphere in hexagonal boron nitride crystal, forming one Enhance displacement doping of the Mg in hexagonal boron nitride lattice while new acceptor level, and then enhances hexagonal boron nitride film p Type electric conductivity, includes the following steps:
1) formation in the vacancy B:
1. chemical gas-phase deposition system is arranged, including outer tube and inner tube, said inner tube is sheathed on outer tube and length is short In outer tube, said inner tube sets BN predecessor warm area, is equipped with BN predecessor in BN predecessor warm area, the BN predecessor be containing B and Compound containing N or the simultaneously inorganic or organic compound containing B, N；Between the outlet end of said inner tube and the outlet end of outer tube Region forms reaction chamber, is equipped with growth substrates in the reaction chamber；
2. the formation of rich nitrogen atmosphere: forming rich nitrogen atmosphere by carrier gas, the carrier gas includes gas containing N or gaseous mixture containing N Body；
3. the growth of substrate: adjusting the vacuum degree of chemical gas-phase deposition system to 10-4Torr is hereinafter, be passed through protective gas pair Substrate carries out 800~1000 DEG C of 20~60min of annealing；After the completion of annealing, the temperature of BN predecessor warm area is promoted to 85 ~100 DEG C, reaction chamber temperature is promoted to 1050~1060 DEG C；It is passed through the carrier gas of rich nitrogen by inner tube, carries BN predecessor to growth Substrate is reacted, and because rich nitrogen condition can break B, N ratio, is formed more vacancy B, be can be used as acceptor level in h-BN, And its energy level more than valence band~150meV, thus a new acceptor level can be provided, six sides containing a large amount of vacancy B are made Boron nitride pellicle；
2) p-type doping:
The source Mg warm area is set in chemical gas-phase deposition system, for the source Mg predecessor, the source the Mg predecessor packet to be arranged Include nitridation magnesium dust, magnesium powder；The temperature of the source Mg warm area is promoted to 700~800 DEG C, the source Mg predecessor is carried to containing by carrier gas The hexagonal boron nitride film in the vacancy B is reacted；Reaction terminates, the cooled to room temperature in protective gas, and Mg displacement is made The p-type hexagonal boron nitride film of doping.
In a preferred embodiment of the present invention, the source Mg warm area is set to inner tube, and positioned at BN predecessor warm area and instead It answers between room.
In a preferred embodiment of the present invention, the solid state reagents that the BN predecessor mixes for B, N, including borazane, At least one of borazine powder.
In a preferred embodiment of the present invention, the growth substrates use metallic film substrate or other semiconductor substrates, The metallic film substrate be copper foil, platinum foil, nickel foil elemental metals substrate or in which at least two alloy substrates, it is described Semiconductor substrate is Si, SiO2, GaAs, sapphire, GaN substrate.
In a preferred embodiment of the present invention, the carrier gas includes at least one in hydrogen, argon gas and ammonia or nitrogen Kind, wherein the volume flow of ammonia or nitrogen is 10~50sccm.
In a preferred embodiment of the present invention, the protective gas includes hydrogen, argon gas.
In a preferred embodiment of the present invention, with mechanical pump and molecular pump adjust the vacuum degree of chemical gas-phase deposition system to 10-4Torr or less.
In a preferred embodiment of the present invention, the BN predecessor warm area, the source Mg predecessor warm area and reaction chamber length are 25~35cm, 8~12cm of center are flat-temperature zone.
In a preferred embodiment of the present invention, the BN predecessor warm area, the source Mg predecessor warm area and reacting chamber space have every Hot material is filled up, for obstructing the adjacent mutual heat affecting of warm area part.
In a preferred embodiment of the present invention, the BN predecessor warm area, the source Mg predecessor warm area and reaction chamber are connected with Independent temperature system and flow controller control temperature and gas flow by computer control system.
The technical program compared with the background art, it has the following advantages:
1. the rich nitrogen atmosphere effect of this programme first is that break original B, N ratio, generate more vacancy B, the vacancy B is in h-BN In can be used as acceptor level, to obtain higher hole concentration, enhance the p-type conductance of h-BN；
2. the rich nitrogen atmosphere effect of this programme second is that creating more vacancy B, increasing p-type conductance on the basis of, exist for Mg Displacement doping in h-BN is provided convenience, and how sub so that h-BN is obtained effective Two-Dimensional Hole with higher conductive current P-type thin film structure；
3. this programme passes through effective combination of device, while n-type impurity doping, nitrogen-containing precursor is introduced, to provide One rich nitrogen atmosphere makes to increase the vacancy B and enhancing displacement is entrained in once-through operation and realizes, in conjunction with the parameter control of three warm areas System, has taken into account efficiency and quality well.
Detailed description of the invention
Fig. 1 shows chemical gas-phase deposition system schematic device of the present invention；
Fig. 2 shows the schematic illustrations that the generation in the vacancy B under rich nitrogen atmosphere and Mg doping enter h-BN lattice；
Fig. 3 shows the schematic diagram of transfer process that the h-BN:Mg film grown under rich nitrogen atmosphere is transferred to target substrate；
Fig. 4 shows the SEM figure of surface condition after Mg doped growing under rich nitrogen atmosphere, wherein (a), (b) are respectively The SEM photograph of nitrogen rich atmosphere growth p-type h-BN:Mg film is created using ammonia and nitrogen；
Fig. 5 shows Mg under rich nitrogen atmosphere and adulterates successful XPS figure；
Fig. 6 shows Mg under rich nitrogen atmosphere and adulterates successful AES figure；
Fig. 7 is shown before and after probe platform pictorial diagram and the plated electrode of the h-BN:Mg film grown under rich nitrogen atmosphere H-BN:Mg/SiO2Pictorial diagram；
Fig. 8 shows the electric conductivity that Mg under rich nitrogen atmosphere adulterates Mg doping h-BN film under h-BN film and non-lipid nitrogen atmosphere Comparison diagram.
Specific embodiment
Embodiment 1
Steps are as follows for the present embodiment:
1, three-temperature-zone chemical gas-phase deposition system (Fig. 1) is established:
1) system is made of three independent warm areas and separate gas pipeline.Each warm area is about 30cm, and center 10cm is Flat-temperature zone is respectively filled up between two warm areas with fibrous ceramic insulation (such as asbestos), obstructs the mutual heat affecting between adjacent warm area, And each warm area is controlled by independent temperature control module.
2) big quartz ampoule (outer tube) is used as reaction cavity, and length is longer than three warm area overall lengths, for provide vacuum environment and Simultaneously deposition reaction occurs for whole cavity gaseous environment；Tubule (inner tube) constitutes independent ventilation pipeline, is directly connected with independent gas circuit, Length is arranged and reaction chamber (third warm area) by BN predecessor warm area (the first warm area) and the source Mg warm area (the second warm area), outlet Section start.
3) there is mass flow controller to connect gas cylinder inside and outside outside pipeline, gas mass flow can be made using software accurate Control, and do the mixed gas supply of multiple gases.
4) big quartzy pipe end is connected with vacuum pump by flange, including mechanical pump and molecular pump two-stage vacuum device, Cavity can be evacuated to required vacuum degree, it is ensured that reaction is protected from airborne pollution, while useless by what is generated in reaction process after being sealed Gas and by-product take cavity out of.
2, the synthesis for the p-type h-BN two-dimensional film that Mg is adulterated under rich nitrogen atmosphere, the vacancy B and displacement are doped in an inner tube It is synchronous to carry out；
1) the Cu foil for cutting about 8cm × 8cm, connecting with the mains, it is thick to reduce surface to be put into progress electrochemical polish in electrolyte Rugosity and nucleation density are cleaned and spare after wiped clean.
2) large and small quartz ampoule and wiped clean are cleaned with alcohol and deionized water respectively.
3) Mg is chosen3N2Do doped source, weigh 0.05g be placed on a width less than inner tube diameter, length about 4cm it is small Inside type quartz boat, then using in thin bar push-in tubule, until it be in the center of the second warm area, equally, selection Predecessor of the borazane (ammonia borane) as B, N after weighing 0.0120g, is placed in another small-sized quartz boat and is pushed away To the center of the first warm area；Pretreated Cu foil substrate is finally placed in the center of third warm area.
4) inside and outside two quartz ampoule front ends are connected with flange with gas circuit and vacuum pump respectively with end, benefit after fixing The intracavitary air pressure of tubular type is evacuated to 10 with mechanical pump and molecular pump-4Torr is hereinafter, guarantee that the pollutants such as water, oxygen are clear in air It removes；Then it sets temperature control panel and ventilation and starts to warm up program, when third temperature-raising region temperature raising is to 800-1000 DEG C, outer tube is logical With a certain proportion of hydrogen and argon gas mixed gas (10sccm H2With 20sccm Ar), about 20- is made annealing treatment to substrate 60 minutes, to remove substrate surface oxide layer and other absorption pollutants, increases the domain of Cu to reduce nucleation density greatly, have Conducive to the growth of high-quality thin film.
5) after the completion of annealing, three-temperature-zone reaction chamber temperature is promoted to reaction temperature (1050-1060 DEG C), meanwhile, first and second Warm area is promoted to preset temperature (85-100 DEG C, 700~800 DEG C) respectively, starts growth phase at this time: being changed to be passed through from inner tube 8sccm H2With 20sccm Ar as conveying Borazane and Mg3N2(gas flow and ratio can be according to doping for the carrier gas of steam Concentration and reaction speed need to be scaled)；Importantly, to provide rich nitrogen atmosphere, while being passed through from inner tube a certain amount of NH3Or N2(10-50sccm), three's mixed gas is then as conveying Borazane steam and Mg3N2The carrier gas of steam carries Predecessor to third warm area part mixes, and since rich nitrogen atmosphere has broken the ratio of B:N=1:1, more vacancy B is caused to produce It is raw, so that Mg is easier to enter progress displacement doping in h-BN lattice, to generate the p-type h-BN two-dimensional film (Fig. 2) of high quality.
6) heating schedule is automatically closed after reaction, and changes and continue to be passed through 5sccm H in outer tube2It is used with 20sccm Ar Make protective gas, finally after naturally cooling to room temperature, close vacuum pump, opens after cavity restores vacuum degree and take out sample differentiation Front and back sides are placed in drying box stand-by.
Embodiment 2
Embodiment 2 the difference from embodiment 1 is that: form the vacancy B and displacement doping-sequence and carry out, include the following steps:
1) formation in the vacancy B:
1. chemical gas-phase deposition system is arranged, including outer tube and inner tube, said inner tube is sheathed on outer tube and length is short In outer tube, said inner tube sets BN predecessor warm area, is equipped with BN predecessor in BN predecessor warm area, the BN predecessor be containing B and Compound containing N or the simultaneously inorganic or organic compound containing B, N；Between the outlet end of said inner tube and the outlet end of outer tube Region forms reaction chamber, is equipped with growth substrates in the reaction chamber；
2. the formation of rich nitrogen atmosphere: forming rich nitrogen atmosphere by carrier gas, the carrier gas includes gas containing N or gaseous mixture containing N Body；
3. the growth of substrate: adjusting the vacuum degree of chemical gas-phase deposition system to 10-4Torr is hereinafter, be passed through protective gas pair Substrate carries out 800~1000 DEG C of 20~60min of annealing；After the completion of annealing, the temperature of BN predecessor warm area is promoted to 85 ~100 DEG C, reaction chamber temperature is promoted to 1050~1060 DEG C；It is passed through the carrier gas of rich nitrogen by inner tube, carries BN predecessor to growth Substrate is reacted, and because rich nitrogen condition can break B, N ratio, is formed more vacancy B, be can be used as acceptor level in h-BN, And its energy level more than valence band~150meV, thus a new acceptor level can be provided, six sides containing a large amount of vacancy B are made Boron nitride pellicle；
2) p-type doping:
The source Mg warm area is set in chemical gas-phase deposition system, for the source Mg predecessor, the source the Mg predecessor packet to be arranged Include nitridation magnesium dust, magnesium powder；The temperature of the source Mg warm area is promoted to 100~800 DEG C, the source Mg predecessor is carried to containing by carrier gas The hexagonal boron nitride film in the vacancy B is reacted；Reaction terminates, the cooled to room temperature in protective gas, and Mg displacement is made The p-type hexagonal boron nitride film of doping.
For the feasibility and beneficial effect for verifying this programme, the two-dimentional h-BN film of this programme p-type doping is shifted And test analysis.
1) transfer (Fig. 3) of p-type h-BN two-dimensional film:
Generally use transfer method of the PMMA (polymethyl methacrylate) as medium.It is laid in hexagonal boron nitride One layer of PMMA protects boron nitride, and lower growth substrate copper sheet passes through ammonium persulfate ((NH4)2S2O8) solution removal, obtain PMMA The hexagonal boron nitride film floating of covering is on etching solution, to be transferred to other target substrates after rinsing in deionized water On, it is then heating and curing, the hexagonal boron nitride film for covering PMMA is sufficiently contacted with target substrate, and sample is placed in third PMMA is removed in ketone solution, just completes the transfer process of hexagonal boron nitride.
2) scanning electron microscope (SEM) analysis (Fig. 4):
It is due to one from SEM figure (Fig. 4) as can be seen that the signified part of green arrow is some folds (Wrinkles) Complete h-BN film is engaged, its coefficient of expansion and the coefficient of expansion of copper foil are to can also be used as caused by difference and judge h-BN The qualitative criteria whether film covers with；Pink colour arrow meaning is the nucleating point of h-BN monocrystalline, is clear that using NH3Wound Nitrogen atmosphere of getting rich can be such that nucleation density increases, and use N in contrast2The sample of rich nitrogen atmosphere is created both topographically to h-BN's Nucleating growth does not influence essential influence.
3) XPS and AES carries out composition test analysis (Fig. 5~Fig. 6) to it:
Transfer to SiO2H-BN on/Si substrate is tested using XPS spectrum, to determine the elemental composition of film.Use C After element carries out calibration to power spectrum, which is obtained by Gauss curve fitting, obtains the peak position of N1s and B1s respectively 398.2 And 190.7eV, in addition, there is also a small peaks, and corresponding to table from xps energy spectrum element can find at 49.2eV, which is Mg Auger peak where.
But whether this Mg element peak, which is the Mg atom for from surface impurity particle rather than mixing h-BN lattice, is contributed, and is needed Further to judge by AES power spectrum: it can be found that three obvious peak positions, respectively correspond from AES spectra measurement result Mg element peak intensity measured by the sample grown under the Auger peak position of B KLL, N KLL, Mg KLL, rich nitrogen atmosphere relatively before Sample is enhanced, and illustrates that the doping in h-BN lattice of Mg can be enhanced in rich nitrogen atmosphere.
4) electrical testing analysis (Fig. 7~Fig. 8) is carried out to it using sonde method:
Whether electrical testing is one of the most important characterization carried out to the h-BN film after doping, look at it from insulation Semiconductor is changed into p-type electric-conducting film, and judges whether rich nitrogen atmosphere enhances its electric conductivity.
We use Single probe rectification method first, in h-BN:Mg/SiO2Pt electrode is deposited in four angles of sample, moves back at 400 DEG C Fiery 20 minutes realization Ohmic contacts；Pt electrode is contacted with a tungsten tipped probe again, another tungsten tipped probe directly contacts h-BN:Mg film Surface forms Schottky contacts, and I-V curve only electric current just occurs in the case where negative voltage, it is thus determined that its conduction type For p-type, i.e. its majority carrier is hole.
Secondly, having comparative h-BN, h-BN:Mg and h-BN:Mg (N-rich) sample to one group using probe platform Carried out electrical testing respectively: firstly, for undoped h-BN sample, I-V curve is insulating properties, illustrates that h-BN film is Insulation film；Under 3V voltage, h-BN:Mg sample surfaces electric current reaches 10mA magnitude；And the electricity of h-BN:Mg (N-rich) sample Stream then has apparent increase, has broken the ratio of B:N=1:1 predictive of the rich nitrogen atmosphere that we design, h-BN is caused to grow During produce more vacancy B, while Mg being made to be easier to enter and carry out displacement doping in h-BN lattice, to generate height The p-type h-BN two-dimensional film of quality.
In addition, by measuring its mobility, carrier concentration, the main parameters such as activation energy verify solution p-AlN and are difficult to connect The problem of touching, and apply in deep ultraviolet LED component, its p-type electrical pumping efficiency and light extraction efficiency are promoted with it, it will be following purple Possess powerful advantage on outer shortwave opto-electronic device.
Skilled person will appreciate that when technical parameter of the invention changes in the following range, it is contemplated that obtain Same as the previously described embodiments or similar technical effect:
The richness nitrogen atmosphere can directly or indirectly be reacted generation by the solid, liquid, gas body substance containing N element, described to contain N Substance include: ammonia (NH3), nitrogen (N2), urea or other gases containing N and their one or more substance it Mixing.
The doped source is the substance containing p-type impurity element, including for B impurity and replaces N impurity.It is described to replace B impurity packet Simple substance or compound-material containing low major element (such as the second main group or the first main group) are included, can be solid-state, liquid or gaseous state Substance；It is described for N impurity include simple substance or compound-material containing low major element (such as the 4th main group), can be solid-state, liquid State or gaseous material.
The BN predecessor is the solid state reagents of B, N mixing, including at least one in borazane, borazine powder Kind.
The growth substrates use metallic film substrate or other semiconductor substrates, the metallic film substrate be copper foil, Platinum foil, nickel foil elemental metals substrate or in which at least two alloy substrates, the semiconductor substrate are Si, SiO2、 GaAs, sapphire, GaN substrate.
The CVD system is that two or more gaseous starting materials import in same reaction chamber, and then they are mutual Between in certain temperature environment issue biochemical reaction, eventually form final required solid material, and deposit to preset lining Bottom surface；The gaseous starting materials can directly or indirectly be occurred by gaseous state, solid-state, liquid source.The CVD system can be letter Single CVD, plasma enhanced CVD, the homogeneous systems such as metallorganic CVD (MOCVD).
The above is only the preferred embodiment of the present invention, the range implemented of the present invention that therefore, it cannot be limited according to, i.e., according to Equivalent changes and modifications made by the invention patent range and description, should still be within the scope of the present invention.

Claims (10)

1. a kind of method of richness nitrogen atmosphere enhancing boron nitride pellicle p-type electric-conducting doping, it is characterised in that: first by first in rich nitrogen Promote the acceptor level for forming the vacancy B in hexagonal boron nitride crystal under atmosphere, then passes through Mg replacing in hexagonal boron nitride lattice Position doping, the two carry out in order, and then enhance hexagonal boron nitride film p-type conductivity energy；Include the following steps:
1) formation in the vacancy B:
1. chemical gas-phase deposition system is arranged, including outer tube and inner tube, said inner tube is sheathed on outer tube and is shorter in length than outer Pipe, said inner tube set BN predecessor warm area, and BN predecessor is equipped in BN predecessor warm area, and the BN predecessor is containing B and containing N's Compound or the simultaneously inorganic or organic compound containing B, N；Region shape between the outlet end of said inner tube and the outlet end of outer tube At reaction chamber, growth substrates are equipped in the reaction chamber；
2. the formation of rich nitrogen atmosphere: forming rich nitrogen atmosphere by carrier gas, the carrier gas includes gas containing N or mixed gas containing N；
3. the growth of substrate: adjusting the vacuum degree of chemical gas-phase deposition system to 10-4Torr is hereinafter, be passed through protective gas to substrate Carry out 800~1000 DEG C of 20~60min of annealing；After the completion of annealing, the temperature of BN predecessor warm area is promoted to 85~100 DEG C, reaction chamber temperature is promoted to 1050~1060 DEG C；Be passed through the carrier gas of rich nitrogen by inner tube, carry BN predecessor to growth substrates into Row reaction, is made the hexagonal boron nitride film in the vacancy containing B；
2) p-type doping:
The source Mg warm area is set in chemical gas-phase deposition system, and for the source Mg predecessor to be arranged, the source Mg predecessor includes nitrogen Change magnesium dust, magnesium powder；The temperature of the source Mg warm area is promoted to 700~800 DEG C, it is empty to B is contained to carry the source Mg predecessor by carrier gas The hexagonal boron nitride film of position is reacted；Reaction terminates, the cooled to room temperature in protective gas, and Mg displacement doping is made P-type hexagonal boron nitride film.
2. a kind of method of rich nitrogen atmosphere enhancing boron nitride pellicle p-type electric-conducting doping according to claim 1, feature exist In: the source Mg warm area is set to inner tube, and between BN predecessor warm area and reaction chamber.
3. a kind of method of rich nitrogen atmosphere enhancing boron nitride pellicle p-type electric-conducting doping according to claim 1, feature exist In: the BN predecessor is at least one of the solid state reagents, including borazane, borazine powder of B, N mixing.
4. a kind of method of rich nitrogen atmosphere enhancing boron nitride pellicle p-type electric-conducting doping according to claim 1, feature exist Use metallic film substrate or other semiconductor substrates in: growth substrates, the metallic film substrate be copper foil, platinum foil, Nickel foil elemental metals substrate or in which at least two alloy substrates, the semiconductor substrate are Si, SiO2, GaAs, Lan Bao Stone, GaN substrate.
5. a kind of method of rich nitrogen atmosphere enhancing boron nitride pellicle p-type electric-conducting doping according to claim 1, feature exist It include hydrogen, argon gas and at least one of ammonia or nitrogen in: the carrier gas, wherein the volume flow of ammonia or nitrogen is 10~50sccm.
6. a kind of method of rich nitrogen atmosphere enhancing boron nitride pellicle p-type electric-conducting doping according to claim 1, feature exist In: the protective gas includes hydrogen, argon gas.
7. a kind of method of rich nitrogen atmosphere enhancing boron nitride pellicle p-type electric-conducting doping according to claim 1, feature exist In: with the vacuum degree of mechanical pump and molecular pump adjusting chemical gas-phase deposition system to 10-4Torr or less.
8. a kind of method of rich nitrogen atmosphere enhancing boron nitride pellicle p-type electric-conducting doping according to claim 1, feature exist In: the BN predecessor warm area, the source Mg predecessor warm area and reaction chamber length are 25~35cm, and 8~12cm of center is flat-temperature zone.
9. a kind of method of rich nitrogen atmosphere enhancing boron nitride pellicle p-type electric-conducting doping according to claim 1, feature exist In: the BN predecessor warm area, the source Mg predecessor warm area and reacting chamber space have heat-barrier material to fill up, for obstructing adjacent warm area part Mutual heat affecting.
10. a kind of method of rich nitrogen atmosphere enhancing boron nitride pellicle p-type electric-conducting doping according to claim 1, feature Be: the BN predecessor warm area, the source Mg predecessor warm area and reaction chamber are connected with independent temperature system and flow controller, lead to Cross computer control system control temperature and gas flow.
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CN103972332A (en) * 2013-01-31 2014-08-06 山东浪潮华光光电子股份有限公司 P-type gallium nitride material hole activating method
CN104233454A (en) * 2014-06-17 2014-12-24 中山大学 Method for effectively synthesizing monocrystal hexagonal boron nitride structure by substitution reaction
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